Bilayer Formation Research Articles

Stereoselectivity in spontaneous assembly of rolled incommensurate carbon bilayers

The periodicity of two-dimensional entities can be manipulated by their stacking assembly, and incommensurate stacks of bilayers are attracting considerable interest in materials science. Stereoisomerism in incommensurate bilayers was first noted with incommensurate double-wall carbon nanotubes composed of helical carbon networks, but the lack of structural information hampered the chemical understanding such as the stereoselectivity during bilayer formation. In this study, we construct a finite molecular version of incommensurate carbon bilayers by assembling two helical cylindrical molecules in solution. An outer cylindrical molecule is designed to encapsulate a small-bore helical cylindrical molecule, and the spontaneous assembly of coaxial complexes proceeds in a stereoselective manner in solution with a preference for heterohelical combinations over diastereomeric, homohelical combinations. The rational design of incommensurate bilayers for material applications may be facilitated by the design and development of molecular versions with discrete structures with atomic precision.

First-principles study on electronic properties of twisted bilayer borophene

Borophene has received considerable investigations in recent five years that it is reported to possess a series of marvelous properties. However, most of the researches are about its monolayer form, the bilayer borophene, especially the twisted bilayer form which is a hot topic recently, has not been studied in detail. Herein, the first-principles calculations based on the density functional theory (DFT) method was performed to study the electronic properties of three kinds of twisted bilayer borophene that each kind of bilayer borophene is twisted to a certain angle in the plane. For the consideration of structural stability and calculation cost, the bilayer borophene are optimized to be 32.2°, 58.0° and 83.6° using an algorithm based on crystal matching theory. The charge density of relaxed twisted bilayer borophene shows the proximity of boron atoms. The analysis of band structure reveals that the twisted bilayer structure could separate the degenerate band and transform the bands to direct type, thus, modulating the resistance. In addition, a near-zero density of states could be found when bilayer borophene is twisted. This research could provide a basis for the applications of borophene, such as integrated electronic devices and micro/nano electronics.

Rapid fabrication of teflon apertures by controlled high voltage pulses for formation of free standing planar lipid bilayer membrane.

Free standing artificial lipid bilayers are widely used in the study of biological pores. In these types of studies, the free standing planar lipid bilayer is formed over a micron-sized aperture consisting of either polymer such as Polytetrafluoroethylene (PTFE, Teflon) or glass. Teflon is chemically inert, has a low dielectric constant, and has a high electrical resistance which combined allow for obtaining low noise recordings. This study investigates the reproducible generation of micropores in the range of 50-100 microns in diameter in a Teflon film using a high energy discharge set-up. The discharger set-up consists of a microprocessor, a transformer, a voltage regulator, and is controlled by a computer. We compared two approaches for pore creation: single and multi-pulse methods. The results showed that the multi-pulse method produced narrower aperture size distributions and is more convenient for lipid bilayer formation, and thus would have a higher success rate than the single-pulse method. The bilayer stability experiments showed that the lipid bilayer lasts for more than 33h. Finally, as a proof-of-concept, we show that the single and multi-channel electrophysiology experiments were successfully performed with the apertures created by using the mentioned discharger. In conclusion, the described discharger provides reproducible Teflon-pores in a cheap and easy-to-operate manner.

In vitro therapeutic evaluation of nanoliposome loaded with Xyloglucans polysaccharides from Tamarindus flower extract

Nanoparticles are interesting area of research developed for several diagnostic and therapeutic applications. Tamarind flower extract is rich in Xyloglucan, a starch like polysaccharide which promotes proliferation and various application areas like drug-delivery technology. In recent years researchers are evaluating nanoliposome using in vitro and in vivo studies to discover their biomedical applications. Considering the importance and feasibility of nanoliposome, the present study is focused on synthesis of liposomes via biological method. The biological molecules of Tamarindus indica flower were used for the synthesis of nanoliposome. The synthesized Tamarindus indica flower extract lipid nanoparticles (TifeLiNPs) loaded with xyloglucans were characterized and evaluated for therapeutic applications (antibacterial, antioxidant, antidiabetic, anticancer and anti-inflammatory activities) under in vitro condition. UV‐Vis spectral analysis revealed the emission of peak at 232 nm. Further, the chemical characterization using FTIR revealed the presence of components in the functional group. EDX analysis exhibited the presence of O, Na, P and Cl, while DLS confirmed bilayer formation of xyloglucan and liposomes with uniform size (70–80 nm) and spherical shape. The Physicochemical characterization of tamarind flower extract for its chemical composition revealed the presence of carbohydrates, alkaloids, terpenoids, glycosides, saponins, tannins and flavonoids in confirmatory test. Presence of carbohydrate polymers such as rhamnose, arabinose, galactose, glucose and xylose revealed using high performance anion exchange (HPAE) chromatography under basic conditions on an ion chromatographic system were measured using Pulsed Amperometric Detection (PAD). The synthesized nanoliposome evaluated against Gram negative and Gram positive bacteria showed potential antibacterial activity. TifeLiNPs demonstrated significant in vitro antioxidant potential, antidiabetic, anti-cancer and anti-inflammatory activity. Overall, the present study exhibited the potential application of TifeLiNPs for biomedical purposes.

Probing Molecular Mechanisms during the Oscillatory Adsorption of Propyl Chain Functionalized Organosilane Films with Sum Frequency Generation Spectroscopy.

The selectivity rules of sum frequency generation spectroscopy were exploited to determine propyl chain order during the time-dependent oscillatory adsorption of propyltrimethoxysilane (PTMS) and Langmuir-type growth of propyldimethylmethoxysilane (PDMMS). During the early stages of film growth, molecular packing density determines the extent of propyl chain defects within both films with high surface coverage resulting in a film with fewer defects. Following this, an ordered monolayer-like film stabilizes on the Al2O3 substrate for both silanes. Although this result is intuitive for the Langmuir-type growth of PDMMS, the stabilization of molecular ordering despite the continuing oscillation in PTMS surface coverage indicates the presence of a stable monolayer, while it is the oligomerized PTMS dendrimers which continue to desorb and readsorb to the substrate. We also reveal for the first time, the formation of a physisorbed bilayer during the self-assembly process of PTMS. The presence of this ordered, physisorbed bilayer on top of the covalently bound PTMS film plays a key role in the process of the molecular self-assembly mechanism and is proposed to enable further condensation of the covalently bound film.

Influence of Sensor Coating and Topography on Protein and Nanoparticle Interaction with Supported Lipid Bilayers.

Supported lipid bilayers (SLBs) have proven to be valuable model systems for studying the interactions of proteins, peptides, and nanoparticles with biological membranes. The physicochemical properties (e.g., topography, coating) of the solid substrate may affect the formation and properties of supported phospholipid bilayers, and thus, subsequent interactions with biomolecules or nanoparticles. Here, we examine the influence of support coating (SiO2 vs Si3N4) and topography [sensors with embedded vs protruding gold nanodisks for nanoplasmonic sensing (NPS)] on the formation and subsequent interactions of supported phospholipid bilayers with the model protein cytochrome c and with cationic polymer-wrapped quantum dots using quartz crystal microbalance with dissipation monitoring and NPS techniques. The specific protein and nanoparticle were chosen because they differ in the degree to which they penetrate the bilayer. We find that bilayer formation and subsequent non-penetrative association with cytochrome c were not significantly influenced by substrate composition or topography. In contrast, the interactions of nanoparticles with SLBs depended on the substrate composition. The substrate-dependence of nanoparticle adsorption is attributed to the more negative zeta-potential of the bilayers supported by the silica vs the silicon nitride substrate and to the penetration of the cationic polymer wrapping the nanoparticles into the bilayer. Our results indicate that the degree to which nanoscale analytes interact with SLBs may be influenced by the underlying substrate material.

Ionic Liquid-Induced Phase-Separated Domains in Lipid Multilayers Probed by X-ray Scattering Studies.

A cellular membrane, primarily a lipid bilayer, surrounds the internal components of a biological cell from the external components. This self-assembled bilayer is known to be perturbed by ionic liquids (ILs) causing malfunctioning of a cellular organism. In the present study, surface-sensitive X-ray scattering techniques have been employed to understand this structural perturbation in a lipid multilayer system formed by a zwitterionic phospholipid, 1,2-dipalmitoyl-sn-glycero-3-phosphocholine. The ammonium and phosphonium-based ILs with methanesulfonate anions are observed to induce phase-separated domains in the plane of a bilayer. The lamellar X-ray diffraction peaks suggest these domains to correlate across the bilayers in a smectic liquid crystalline phase. This induced IL-rich lamellar phase has a very low lamellar repeat distance, suggesting the formation of an interdigitated bilayer. The IL-poor phase closely related to the pristine lipid phase shows a decrement in the in-plane chain lattice parameters with a reduced tilt angle. The ammonium and phosphonium-based ILs with a relatively bulky anion, p-toluenemethanesulfonate, have shown a similar effect.

Adsorption and Conformation Behavior of Lysozyme on a Gold Surface Determined by QCM-D, MP-SPR, and FTIR.

The physicochemical properties of protein layers at the solid–liquid interface are essential in many biological processes. This study aimed to link the structural analysis of adsorbed lysozyme at the water/gold surface at pH 7.5 in a wide range of concentrations. Particular attention was paid to the protein’s structural stability and the hydration of the protein layers formed at the interface. Complementary methods such as multi-parameter surface plasmon resonance (MP-SPR), quartz crystal microbalance with energy dissipation (QCM-D), and infrared spectroscopy (FTIR) were used for this purpose. The MP-SPR and QCM-D studies showed that, during the formation of a monolayer on the gold surface, the molecules’ orientation changes from side-on to end-on. In addition, bilayer formation is observed when adsorbing in the high-volume concentration range >500 ppm. The degree of hydration of the monolayer and bilayer varies depending on the degree of surface coverage. The hydration of the system decreases with filling the layer in both the monolayer and the bilayer. Hydration for the monolayer varies in the range of 50–70%, because the bilayer is much higher than 80%. The degree of hydration of the adsorption layer has a crucial influence on the protein layers’ viscoelastic properties. In general, an increase in the filling of a layer is characterized by a rise in its rigidity. The use of infrared spectroscopy allowed us to determine the changes taking place in the secondary structure of lysozyme due to its interaction with the gold surface. Upon adsorption, the content of II-structures corresponding to β-turn and random lysozyme structures increases, with a simultaneous decrease in the content of the β-sheet. The increase in the range of β-turn in the structure determines the lysozyme structure’s stability and prevents its aggregation.

Hematite/Polystyrene Raspberry‐Like Microcomposites as Stable Support for Silver Nanoparticle Immobilization

AbstractAmong the methods utilized for the preparation of raspberry‐like microcomposites, due to its simplicity and universality, the electrostatically‐driven deposition of nanoparticles at the surface of microparticles is especially attractive. This process, leading to the formation of a single nanoparticle monolayer, is widely reported. On the other hand, no data concerning the electrostatically‐driven formation of nanoparticle bilayers at the surface of microparticles are reported. To fill this gap, the detailed investigation of the formation of silver/hematite nanoparticle bilayers at the surface of polystyrene microparticles is reported. First, the hematite/polystyrene raspberry‐like microcomposites are obtained by immobilization of hematite nanoparticles under an electrostatically‐driven process. The stability of hematite/polystyrene microcomposites at elevated temperatures up to 323 K is monitored using microelectrophoresis. No significant changes in the hematite nanoparticle layer coverage are observed after prolonged time of incubation. This proves the irreversible character of nanoparticle immobilization. Next, the hematite/polystyrene microcomposites are utilized as the interfaces for immobilization of negatively charged silver nanoparticles. This process is quantitatively described using electrokinetic measurements. The changes in the hydrodynamic diameter of microcomposites are also determined. Finally, the validity of the electrokinetic model used in this work for predicting the zeta potential of the silver/hematite/polystyrene microcomposites is confirmed.

Solvent‐Assisted Lipid Bilayer Formation on Au Surfaces: Effect of Lipid Concentration on Solid‐Supported Membrane Formation

Solvent‐assisted lipid bilayer (SALB) formation is emerged as a versatile approach in forming supported lipid membranes (SLBs) on metal surfaces, interesting platforms for transducing a biological signal to an electrical readout where vesicle rupture is not straightforward. Herein, the effect of the lipid concentration in the organic solvent, a key parameter controlling SALB, is addressed in the low and high concentration limits of 1,2‐dipalmitoyl‐sn‐glycero‐3‐phosphocholine lipid on a Au surface. Quartz crystal microbalance with dissipation (QCM‐D) responses are correlated with atomic force microscopy (AFM) topographic and nanomechanical measurements. Upon SALB completion at both concentrations, QCM‐D and AFM topographical characterization suggest the formation of thin, although incomplete, lipid layers at the Au–liquid interface, with frequency and dissipation plateau values departing from well‐established homogeneous SLB responses. Nanomechanical analysis reveals the presence of mostly monolayers at low concentration due to lack of lipid material, while at high concentration excess of lipid material leads to the coexistence of diverse structures. Their formation stems from the SALB formation mechanism, based on lyotropic transformations upon solvent exchange, which differs from customarily vesicle rupture. Such mechanism leads to peculiar two‐step features in approach force curves on SLBs pointing toward a decoupling in bilayer leaflets when supported.

Efficient Lipid Bilayer Formation by Dipping Lipid-Loaded Microperforated Sheet in Aqueous Solution

This paper describes a method for a bilayer lipid membrane (BLM) formation using a perforated sheet along with an open chamber. Microscopic observation of the formed membrane showed a typical droplet interface bilayer. We proved that the formed membrane was a BLM based on electrical measurements of the membrane protein α-hemolysin, which produces nanopores in BLMs. Unlike the conventional approach for BLM formation based on the droplet contact method, this method provides aqueous surfaces with no organic solvent coating layer. Hence, this method is suitable for producing BLMs that facilitate the direct addition of chemicals into the aqueous phase.

Reactive Bilayers by Self-activated Electroless Nickel-Phosphorous Deposition on Pure Aluminum

Nickel-aluminum bilayers and multilayers are commonly used in reactive systems because of their high heat of mixing. Traditionally, the layers are sputter deposited, an expensive and time-consuming process. In this article, a chemical reduction technique, electroless nickel-phosphorous (EN) deposition, is used for formation of the Ni-Al bilayer using a pure Al substrate. Traditionally, EN deposition on Al requires surface activation due to the native oxide layer. Here, we tune the bath pH to dissolve this oxide layer, such that deposition can be obtained without surface activation. Deposition kinetics is measured by tracking the mass change with time and temperature, and we extracted the activation energies at two different pH values. At pH 7, the energy is 98.7 kJ/mol and reduces to 55 kJ/mol at a pH of 8. The process can also be extended to aluminum powders and flakes in order to form reactive core–shell structures.

Reply to the 'Comment on "Bi-layering at ionic liquid surfaces: a sum-frequency generation vibrational spectroscopy- and molecular dynamics simulation-based study"' by M. Deutsch, O. M. Magnussen, J. Haddad, D. Pontoni, B. M. Murphy and B. M. Ocko, Phys. Chem. Chem. Phys., 2021, DOI.

In our recent paper titled "Bi-layering at ionic liquid surfaces: a sum-frequency generation vibrational spectroscopy- and molecular dynamics simulation-based study" co-authored by T. Iwahashi, T. Ishiyama, Y. Sakai, A. Morita, D. Kim, and Y. Ouchi, Phys. Chem. Chem. Phys., 2020, 22, 12565 (hereafter referred to as IW), the sum-frequency (SF) spectra for a homologous series of 1-alkyl-3-methylimidazolium bis(trifluoromethanesulfonyl)amide ([Cnmim][TFSA] n = 4, 6, 8, 10, and 12) were reported. In particular, a clear decrease in the SF signals from the [TFSA]- anions with increasing chain length of the [Cnmim]+ cation (Fig. 5 of IW) was explained in terms of "head-to-head" bi-layer formation at the air/ionic liquid (IL) interface. A comment by M. Deutsch et al. (hereafter referred to as DE) questioned this report, claiming that our proposed structure is not consistent with a multilayered electron density (ED) profile obtained by X-ray reflectivity (XR).

The role of temperature in the formation of human-mimetic artificial cell membranes using droplet interface bilayers (DIBs).

Droplet interface bilayers (DIBs) have recently started to be used as human-mimetic artificial cell membranes. DIBs are bilayer sections created at the interface of two aqueous droplets, such that one droplet can be used as a donor compartment and the other as an acceptor compartment for the quantification of molecular transport across the artificial cell membrane. However, synthetic phospholipids are overwhelmingly used to create DIBs instead of naturally derived phospholipids, even though the diverse distribution of phospholipids in the latter is more biomimetic. We present the first systematic study of the role of temperature in DIB formation, which shows that the temperature at which DIBs are formed is a key parameter for the formation of DIBs using naturally derived phospholipids in a microfluidic platform. The phospholipids that are most abundant in mammalian cell membranes (phosphatidylcholine (PC), phosphatidylethanolamine (PE), phosphatidylserine (PS), and phosphatidylinositol (PI)) only form DIBs when the temperature is above the phase transition temperature (Tm). Similarly, DIB formation usually only occurs above the highest Tm of a single phospholipid in a bespoke formulation. In addition, we show a new phenomenon wherein the DIB "melts" without disintegrating for bilayers formed predominantly of phospholipids that occupy cylindrical spaces. We also demonstrate differences in DIB formation rates as well as permeability of these biomimetic membranes. Given the difficulties associated with making DIBs using naturally derived phospholipids, we anticipate this work will illuminate the role of phospholipid phase transition in mono- and bilayer formation and lay the foundation for DIBs to be used as human-mimetic artificial cell membranes.

Quartz Crystal Microbalance with Dissipation Monitoring (QCM-D): Preparing Functionalized Lipid Layers for the Study of Complex Protein-Ligand Interactions.

Quartz crystal microbalance with dissipation monitoring (QCM-D) is one of the most widely used techniques for the deposition of lipid layers and provides a useful tool for protein-ligand analysis. By using functionalized lipids, for example, with nitrilotriacetic acid (NTA) or biotin, one can couple a molecule to the surface to investigate ligand interactions. Using lipid layers in this way allows for the analysis of complex binding events such as conformational changes, fibrillation, and hierarchical clustering on the surface, which is difficult to interpret with conventional surface sensor techniques. Deposition of lipids and subsequent molecular interactions are easily monitored using both the frequency and the dissipation, which have distinct features in bilayer formation and make QCM-D the ideal technique to use. Here we describe the formation of biotinylated lipid bilayers using two different types of lipids and the subsequent addition of avidin, which can then be used as a basis for linking biotinylated molecules to the surface. These protocols can be adapted to use other lipid moieties and linking chemistries.

Preparation of graphene reinforced aluminium composites: investigation of microstructural, electrical conductivity and microhardness behaviour

We have prepared composites of Al-graphene (0.1 wt%-0.3 wt%) by employing a specially designed dry planetary ball milling technique (by six hrs of milling) followed by optimised compaction of 140 MPa and sintered at 560°C. Various characterisation of composites were carried out by using XRD, XPS, FESEM, TEM, HRTEM, SAED, EDS, micro Raman, electrical conductivity and microhardness analysis to produce an optimised and advanced Al-graphene composite. Graphene grown in typical Al-graphene (0.3 wt%) composite was marked in bi-layer form. EDS shows purity of composite, exhibiting only peaks of Al and C. Results obtained from XRD, XPS, HRTEM and SAED studies confirm the successful formation of composite between Al and graphene without any appearance of aluminium carbide. The typical aluminium-graphene (0.3 wt%) composite exhibits significantly more electrical (56.2 × 106 S/m) and microhardness (157 ± 12 VHN) values than that of pure aluminium.

Preparation of graphene reinforced aluminium composites: investigation of microstructural, electrical conductivity and microhardness behaviour

We have prepared composites of Al-graphene (0.1 wt%-0.3 wt%) by employing a specially designed dry planetary ball milling technique (by six hrs of milling) followed by optimised compaction of 140 MPa and sintered at 560°C. Various characterisation of composites were carried out by using XRD, XPS, FESEM, TEM, HRTEM, SAED, EDS, micro Raman, electrical conductivity and microhardness analysis to produce an optimised and advanced Al-graphene composite. Graphene grown in typical Al-graphene (0.3 wt%) composite was marked in bi-layer form. EDS shows purity of composite, exhibiting only peaks of Al and C. Results obtained from XRD, XPS, HRTEM and SAED studies confirm the successful formation of composite between Al and graphene without any appearance of aluminium carbide. The typical aluminium-graphene (0.3 wt%) composite exhibits significantly more electrical (56.2 × 106 S/m) and microhardness (157 ± 12 VHN) values than that of pure aluminium.

Biomimetic artificial cells to model the effect of membrane asymmetry on chemoresistance.

We present a microfluidic platform that enables the formation of bespoke asymmetric droplet interface bilayers (DIBs) as artificial cell models from naturally-derived lipids. We use them to perform pharmacokinetic assays to quantify how lipid asymmetry affects the permeability of the chemotherapy drug doxorubicin. Previous attempts to model bilayer asymmetry with DIBs have relied on the use of synthetic lipids to achieve asymmetry. Use of natural lipids serves to increase the biomimetic nature of these artificial cells, showcasing the next step towards forming a true artificial cell membrane in vitro. Here we use our microfluidic platform to form biomimetic, asymmetric and symmetric DIBs, with their asymmetry quantified through their life-mimicking degree of curvature. We subsequently examine permeability of these membranes to doxorubicin, and reveal measurable differences in its pharmacokinetics induced by membrane asymmetry, highlighting another factor that potentially contributes to chemoresistance in some forms of cancer.

Cetylpyridinium bromide (CPB)-treated sugarcane bagasse for the removal of chromate in aqueous solution

Modification of sugarcane bagasse (SB) by cetylpyridinium bromide (CPB) creating surfactant-modified SB (SBC) for the removal of chromate has been studied. The CPB adsorbed increased in line with the increased CPB concentrations, and infrared spectroscopy showed preserved SB structure after modification. SB showed little adsorption capacity in the adsorption study; however, the adsorption of chromate is proportional to the amount of CPB adsorbed on SB, possibly due to the attached CPB molecules on the SB. CPB molecules create a bilayer formation on SB, generating anion exchange sites for chromate to be adsorbed on SBC. The adsorption behavior of chromate on SBC followed the Langmuir equation model better than the Freundlich model. A better adsorption capacity was noted at the lower pH value of the chromate solution. In conclusion, surfactant-modified SB could be a potential alternative adsorbent for removing toxic chromate anion in water.

Chirality in porous self-assembled monolayer networks at liquid/solid interfaces: induction, reversion, recognition and transfer.

Chirality in two dimensions (2D) has attracted increasing attention with regard to interesting fundamental aspects as well as potential applications. This article reports several aspects of supramolecular chirality control as exemplified by self-assembled monolayer networks (SAMNs) formed by a class of chiral building blocks consisting of a triangular conjugated core and alkoxy chains on the periphery. It highlights 2D chirality induction phenomena through a classic "sergeants-and-soldiers" mechanism, in which the inducer is incorporated into a network component, as well as through a "supramolecular host-guest" mechanism, in which the inducer is entrapped in the porous space, leading to counterintuitive chirality reversal. Stereochemical control can be extended to three dimensions too, based on interlayer hydrogen bonding of the same class of building blocks bearing hydroxy groups, exhibiting diastereospecific bilayer formation at both single molecule level and supramolecular level arising from orientation between the top and bottom layers. Finally, we showcase that homochiral SAMNs can also be used as templates for the grafting of in situ generated aryl radicals, by covalent bond formation to the basal graphitic surface, thereby yielding topologically chiral functionalized graphite, and thus extending the potential of chiral SAMNs.